DE19959589A1 - Multi-phase detergent tablets - Google Patents

Abstract

Multi-phase automatic dishwashing detergent tablets contain builders, bleaches and optionally other detergent ingredients and a bleach-enhancing active ingredient combination of a water-soluble divalent transition metal salt selected from cobalt, iron, copper and ruthenium and mixtures thereof, a water-soluble ammonium salt, an inert carrier material and optionally contains a peroxygen-based oxidizing agent, wherein the content of the bleach-enhancing active ingredient combination in the individual phases, based on the weight of the phase, is different.

Description

The present invention relates to multi-phase detergent tablets, the one Bleach-enhancing active ingredient combination of a transition metal salt, a Ammonium salt and an oxidizing agent, a method for producing such Shaped body and the use of such an active ingredient combination in multiphase Detergent tablets for automatic dishwashing.

Automatic dishwashing detergents used to clean dishes must have a Effectively eliminate a variety of soiling, such as starchy Stains, grease, tar residues, etc. These include these funds in addition to builders usually enzymes and bleach. The latter must also be used in low-temperature rinses unfold their effect, which is why the agents bleach activators are added. Here but both enzymes and bleach activators are already in action due to the effect of the bleach Detergents can be decomposed, at the same time the bleaching agent to effect The appropriate formulation of these ingredients for product performance is also after Storage is crucial. The problems mentioned are in the offer form compact molded body due to the high density and spatial proximity of the individual Ingredients still reinforced.

There has therefore been no lack of attempts to overcome the problems mentioned.  

For example, European Patent Application EP 481 792 (Unilever) describes laundry detergent tablets, containing a persalt and a bleach activator, wherein the bleach activator is a particular Pseudo-Erstanordnung perhydrolysis must have. This scripture teaches that the Bleaching agents are preferably separated from bleach-destabilizing ingredients should. If the bleach is perborate and a di- or polyacylated amine bleach activator is used, this measure is even mandatory.

European patent application EP 481 793 (Unilever) also describes laundry detergent tablets. These contain sodium percarbonate as a bleaching agent that is resistant to all substances be spatially delimited. Also this writing points explicitly to the Separation of bleach and bleach activator or substances resulting from bleach attack, leading to a loss of bleaching activity.

Another approach for two- or multi-phase washing and Detergent tablets containing bleaches and bleach activators as well contain oxidation-sensitive substances, namely the separation of bleach activators of oxidation-sensitive substances, is in the earlier German patent application DE 198 06 220.6 (Henkel). Thereafter, it is not necessary, the oxidation-sensitive Separate substances spatially from bleach, but the bleach activator. bleach catalysts are explicitly counted in this document to the group of bleach activators.

European Patent Application EP 395 333 (Unilever) describes tabletted Detergent compositions containing sodium perborate and one or more substances from the Group of di- or polyacylated amine bleach activators, enzymes and optical brighteners wherein the persalt is not separated from the substances of this group. The Tablets disclosed in this application are stable and have no loss Bleach or enzyme activity. Bleach catalysts.

Finally, WO 97/03177 (Benckiser) discloses at least two-layered Dishwashing detergent in tablet form, the bleach, bleach activator and Silver protectants are not included, with the bleach and Bleach activator should be contained in a layer. This will improve the cleaning performance tablet-like products because the bleaching agent is not decomposed.  

The older German patent application DE 198 38 127.1 (Henkel) discloses. Automatic dishwashing detergent tablets, the bleaching agents, Bleach activator, perfume and optionally other detergent ingredients. These Both the odor of the product and the odor in the Improve opening of the machine when the tablet consists of at least two phases, wherein the perfume is not in phase with the bleach and bleach activator is included.

The present invention was based on the object, detergent tablets for the To provide automatic dishwashing, characterized by a high performance of the Distinguish a variety of stains, especially bleachable Stains should be achieved even at low rinse temperatures performance benefits. In addition, the detergent tablets to be provided should also be stored suffer no loss of activity and be stable over longer periods of time.

It has now been found that the tasks mentioned by the use of certain Dissolve bleach-enhancing active substance combinations if these are not homogeneous over the distributed throughout the shaped body, but in different phases of the molding in different amount is included.

The present invention is a two- or multi-phase Detergent shaped body for automatic dishwashing containing builders, Bleach and optionally other detergent ingredients, which in addition a Bleach-enhancing combination of a water-soluble salt of a divalent Transition metal selected from cobalt, iron, copper and ruthenium and theirs Mixtures, a water-soluble ammonium salt, an inert carrier material and optionally containing a peroxygen-based oxidizing agent, the content of the Bleach-enhancing active ingredient combination in the individual phases, based on the weight the phase, is different.

The detergent tablets of the invention contain builders, bleaches and a bleach-enhancing active ingredient combination. In addition, they can be more common  Ingredients of detergents included. These substances as well as preferred quantities for the individual substances are described in detail below, with the three mandatory ingredients is started.

The detergent tablets of the invention contain a bleach-enhancing Drug combination. This consists of a water-soluble salt a bivalent one Transition metal selected from cobalt, iron, copper and ruthenium and their Mixtures, a water-soluble ammonium salt and an inert carrier material. Optionally, the drug combination may still be a peroxygen bleach contain. The following is a description of the ingredients of the bleach-enhancing Drug combination. The amounts given here refer to the Active ingredient combination in itself. This combination of active ingredients is an intimate blend of Ingredients present, especially in particulate form bleach-enhancing Combination of active ingredients and is then the shaped bodies according to the invention in the form of a Compounds, preferably a granular compound added.

As a first constituent, the active ingredient combination contains a water-soluble salt of Co ^II , FE ^II , CU ^II , Ru ^II or mixtures thereof. By "water-soluble" is meant here salts which dissolve at room temperature to at least 4 g / l, in particular at least 10 g / l in distilled water.

Preferred divalent transition metal salts include cobalt (II) chloride, which is disclosed in U.S. Pat anhydrous form or can be used as hexahydrate, cobalt (II) sulfate, cobalt (II) - carbonate and cobalt (II) acetate, alone or in mixtures.

The bleach-enhancing agents contained in the detergent tablets according to the invention Active ingredient combination preferably contains 0.01% by weight to 1% by weight, in particular 0.1% by weight. % to 0.5 wt .-% transition metal, each based on the active ingredient combination, wherein Active compound combinations are preferred in which the transition metal salt is a Co salt, especially cobalt (II) chloride. Corresponding inventive Detergent tablets are preferred embodiments of the present invention. The second component of the bleach-enhancing active ingredient combination is a water-soluble Ammonium salt, in amounts of up to 30 wt .-%, based on the active ingredient combination,  can be used. Inventive detergent tablets in which the Bleach-enhancing active ingredient combination 0.5% by weight to 25% by weight, in particular 1% by weight to 10 wt .-% ammonium salt, in each case based on the combination of active ingredients, wherein Active ingredient combinations are preferred in which the ammonium salt a Ammonium halide, sulphate, carbonate, bicarbonate, phosphate, phosphonate, nitrate, perchlorate and / or citrate are preferred in the context of the present invention.

The active ingredient combination may optionally contain peroxygen bleach. These bleaching agents are described below in the ingredients of the invention Detergent tablets described. Detergent tablets according to the invention to which the bleach-enhancing active ingredient combination contained in them contains 1% by weight to 20% by weight. %, in particular 2 wt .-% to 10 wt .-% of peroxide-based oxidizing agent, respectively based on the active ingredient combination contains, wherein drug combinations are preferred where the oxidizing agent is alkali perborate and / or alkali percarbonate, in turn prefers.

The abovementioned active substances of the invention used Active substance combination are in intimate mixture with an inert carrier material. When inert carrier material can be all known to those skilled organic and use inorganic substances, inorganic salts and among these the sulfates, Chlorides, silicates, carbonates, hydrogen carbonates and mixtures thereof are preferred. Detergent tablets preferred according to the invention contain a bleach-enhancing agent Combination of active substances, as inert carrier material alkali sulfate, alkali carbonate, alkali chloride, Contains alkali silicate or mixtures thereof, with the sodium salts are preferred.

Based on the total weight of the detergent tablets according to the invention, that is, on the sum of the weights of the individual phases, the content of the tablets on the active ingredient combination is preferably between 10 ^-5 and 10 wt .-%. This content varies with the content of the active ingredient combination of active substances. For reasons of process economy, however, it is preferred to produce the active substance combination as concentrated as possible and to keep its use concentration in the detergent tablets according to the invention correspondingly low. Preferred detergent tablets according to the invention comprise the bleach-enhancing active ingredient combination in amounts of from 0.0001 to 10% by weight, preferably from 0.001 to 5% by weight, more preferably from 0.005 to 2.5% by weight and in particular from 0.01 to 1 Wt .-%, in each case based on the molding weight.

In the moldings of the invention, the content of the individual phases on the Bleach-enhancing drug combination different. That is, the phases are related on their weight, have different levels of the drug combination. Here are Detergent tablets according to the invention are particularly preferred in which the content of the individual phases of the bleach-enhancing active ingredient combination by more than 0.0001 wt. %, preferably more than 0.001% by weight and in particular more than 0.01% by weight, each based on the weight of the phase, varies.

In the context of the present application, the variation of the surfactant content means more than 0.0001 wt .-%, based on the weight of the individual phases, that the absolute values of the Surfactant content (in wt .-%) in the phases vary by more than 0.0001 wt .-%. Thus, if one phase contains 0.1% by weight of the active ingredient combination, then the content of the other must Phase (s) can be selected so that the width of the variation by the value of 0.1 more than 0.0001 wt .-% is. In other words, is the percentage value of the salary at the Drug combination poorer phase from the percentage number of the salary of each Subtracted drug combination richer phase, the result must be from phase to phase <0.0001. In a four-phase tablet, this would be at a salary at the Active compound combination poorest phase of 0.5 wt .-% (based on the phase) mean that the for example, contents of active ingredient combination of 0.5002% by weight, 0.5004% by weight in the next phases and 0.5006 wt%.

The largest possible differences in the content of drug combination can be characterized achieve that at least one phase contains the bleach-enhancing active ingredient combination, while at least one other phase is free of the bleach-enhancing drug combination is. Corresponding detergent tablets according to the invention are preferred Embodiments of the present invention.

The individual phases of the shaped body can be used in the context of the present invention have different spatial forms. The easiest way to realize this lies in two-layered or multi-layered tablets, each layer of the shaped article representing a phase.  

However, it is also possible according to the invention to produce multiphase shaped bodies in which individual phases take the form of inclusions in (another) phase (s). Next so-called "ring-core tablets" are, for example, coated tablets or Combinations of the embodiments mentioned possible. Examples of multiphase Shaped bodies can be found in the figures of EP-A-0 055 100 (Jeyes), which Toilet cleaning blocks describes. The technically most widespread spatial form multiphase molding is the two- or multi-layer tablet. In the context of the present It is therefore preferred that the phases of the shaped body take the form of layers it being preferred that the detergent tablet be two or three, preferably comprises two layers.

The shaped bodies can assume any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segmented, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, octagonal and octagonal prismatic as well rhombohedral forms are preferred. Also completely irregular bases like arrow or Animal forms, trees, clouds etc. can be realized. Assign the invention Cleaning tablets on corners and edges, so these are preferably rounded. When additional optical differentiation is an embodiment with rounded corners and beveled ("chamfered") edges preferred.

The following is a description of the most important ingredients of the moldings according to the invention, starting with the constituents which are necessarily contained in the molding need: builders and bleach.

In the detergent moldings according to the invention, all customary in Be contained detergents used, in particular, therefore, silicates, Carbonates, organic cobuilders and - where no ecological prejudices against their use exist - also the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} . y is H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates are Na ₂ Si ₂ O ₅ . yH ₂ O is preferred.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

In the context of the present invention, preferred detergent tablets are characterized in that it comprises silicate (s), preferably alkali metal silicates, particularly preferably crystalline ones or amorphous alkali disilicates, in amounts of from 10 to 60% by weight, preferably from 15 to 50% by weight. and in particular from 20 to 40 wt .-%, each based on the weight of Shaped body, included.

The finely crystalline zeolite containing synthetic and bound water is also preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), produced by CONDEA Augusta S. p. A. sold under the brand name VEGOBOND AX® and by the formula

nNa ₂ O. (1-n) K ₂ O. Al ₂ O ₃ . (2-2.5) SiO ₂ . (3.5-5.5) H ₂ O

can be described. The zeolite can be used both as a builder in a granular Compound used, as well as to a kind of "powdering" of the entire to be pressed Mixture be used, whereby usually both ways for the incorporation of the zeolite in the premix can be used. Suitable zeolites have an average particle size of Less than 10 microns (volume distribution, measuring method: Coulter Counter) on and contain preferably 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.

Of course, a use of the well-known phosphates as builders possible, unless such use should be avoided for environmental reasons. Among the multitude of commercially available phosphates are the alkali metal phosphates with particular preference of pentasodium or Pentakaliumtriphosphat (sodium or Potassium tripolyphosphate) in the detergents and cleaning agents industry the greatest importance.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium phosphate, KDP), KH ₂ PO ₄ , is a white salt of 2.33 gcm ^-3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is light soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^{- 3} , water loss at 95 °), 7 moles (density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 moles water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which have a density of 1.62 gcm ^-3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 390% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56 gcm ^-3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises z. Example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals. Na ₄ P ₂ O, formed on heating of disodium phosphate to <200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and the solution is dehydrated by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.

Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.

Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher mol. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (<23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are according to the invention just like sodium tripolyphosphate, potassium tripolyphosphate or Mixtures of these two can be used; also mixtures of sodium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and  Sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and Potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

In the context of the present invention, preferred detergent tablets are characterized characterized in that it contains phosphate (s), preferably alkali metal phosphate (s), especially preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of from 20 to 80% by weight, preferably from 25 to 75% by weight, in particular of 30 to 70 wt .-%, each based on the weight of the base molding, included.

As further constituents alkali carriers may be present. To be considered as alkali carriers for example, alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, Alkali metal sesquicarbonates, said alkali silicates, alkali metal silicates, and mixtures the abovementioned substances, preference being given in the context of this invention to the alkali metal carbonates, especially sodium carbonate, sodium bicarbonate or sodium sesquicarbonate be used. Particularly preferred is a builder system containing a mixture of Tripolyphosphate and sodium carbonate. Also particularly preferred is a builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.

In particularly preferred detergent tablets carbonate (s) and / or Hydrogen carbonate (s), preferably alkali metal carbonates, more preferably sodium carbonate, in Amounts of 5 to 50 wt .-%, preferably from 7.5 to 40 wt .-% and in particular of 10 to 30 wt .-%, each based on the weight of the base molding, included.

As organic cobuilders can in the detergent tablets according to the invention in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) and phosphonates used become. These classes of substances are described below.

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, understood by polycarboxylic acids such carboxylic acids which carry more than one acidity function. For example, these are citric acid, Adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, Sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use of  ecological reasons, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. The acids are next to theirs Builder action typically also the property of an acidifying component and serve thus also for setting a lower and milder pH of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.

As a builder further polymeric polycarboxylates are suitable, these are for example the Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70000 g / mol.

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molar masses M _{W of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, this group may again the short-chain polyacrylates, the molecular weights of 2000 to 10,000 g / mol, and particularly preferably from 3000 to 5000 g / mol, have to be preferred.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As special Copolymers of acrylic acid with maleic acid have proven to be suitable, containing 50 to 90% by weight of % Acrylic acid and 50 to 10 wt .-% maleic acid. Your molecular weight,  based on free acids, is generally from 2000 to 70000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution be used. The content of the (co) polymeric polycarboxylates is preferably 0.5 to 20 wt .-%, in particular 3 to 10 wt .-%.

To improve the solubility in water, the polymers may also be allyl sulfonic acids, such as For example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

Also particularly preferred are biodegradable polymers of more than two various monomer units, for example those containing as monomers salts of acrylic acid and the maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers Salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

Further preferred copolymers are those which preferably contain acrolein as monomers and Acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, as further preferred builder substances are polymeric aminodicarboxylic acids, their To name salts or their precursors. Particularly preferred are polyaspartic acids or their salts and derivatives, in addition to cobuilder properties and a have bleach-stabilizing effect.

Further suitable builder substances are polyacetals which are obtained by reaction of Dialdehydes with Polyolcarbonsäuren, which 5 to 7 C-atoms and at least 3 Hydroxyl groups can be obtained. Preferred polyacetals are made Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from Polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or Polymers of carbohydrates obtained by partial hydrolysis of starches can. The hydrolysis can be carried out by conventional, for example acid or enzyme catalyzed Procedures are performed. Preferably, they are hydrolysis products average molecular weights in the range of 400 to 500,000 g / mol. Here is a polysaccharide with  a dextrose equivalent (DE) in the range of 0.5 to 40, especially from 2 to 30 preferred, DE being a common measure of the reducing effect of a poly saccharides compared to dextrose which has a DE of 100. Useable are both Maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher Molar masses in the range of 2000 to 30,000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Also suitable is an oxidized oligosaccharide. A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

Also oxydisuccinates and other derivatives of disuccinates, preferably Ethylenediamine disuccinate are other suitable cobuilders. This is ethylenediamine-N, N'- disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and Glycerol trisuccinates. Suitable amounts are zeolithhaltigen and / or silicate-containing Formulations at 3 to 15 wt .-%.

Further useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which at least 4 carbon atoms and at least one hydroxy group and a maximum of two Contain acid groups.

Another class of substances with co-builder properties are the phosphonates these are in particular hydroxyalkane or aminoalkanephosphonates. Among the Hydroxyalkane phosphonates is the 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular Meaning as a co-builder. It is preferably used as the sodium salt, the Disodium salt neutral and the tetrasodium salt alkaline (pH 9). When Aminoalkane phosphonates are preferably ethylenediamine tetramethylene phosphonate (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) and their higher homologues in question. They are preferably in the form of neutral sodium salts, eg. B. as Hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The  Aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, especially if the agents also contain bleach, it may be preferred Aminoalkanphosphonate, in particular DTPMP use, or mixtures of the to use said phosphonates.

In addition, all compounds that are capable of complexes with alkaline earth ions train as co-builders.

The amount of builder is usually between 10 and 70 wt .-%, preferably between 15 and 60 wt .-% and in particular between 20 and 50 wt .-%.

As a third essential ingredient in addition to the bleach-enhancing active ingredient combination and builder detergent tablets according to the invention contain bleach. Among the compounds which serve as bleaches and deliver H ₂ O ₂ in water, sodium percarbonate has particular significance. Further useful bleaching agents are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and peroxygenic salts or peracids which yield H ₂ O ₂ , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid. Detergent tablets according to the invention may also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaching agents are the diacyl peroxides, such as. B. dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimido peroxycaproic acid [Phthaloiminoper -oxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamide-operadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.

As a bleaching agent in the inventive detergent tablets for machine Dishwashing can also chlorine or bromine releasing substances are used. Under the suitable chlorine or bromine releasing materials include, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhy danthoin are also suitable.

The bleaching agents are usually used in automatic dishwashing detergents in amounts of from 1 to 30% by weight, preferably from 2.5 to 20% by weight and in particular from 5 to 15% by weight, respectively based on the agent used. In the context of the present invention, the mentioned proportions on the weight of the entire molding.

Bleach activators which aid in the action of the bleaches may also be included be the shaped body according to the invention. Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of Anhydrides, esters, imides and acylated imidazoles or oximes. examples are Tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylene diamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5- triazine DADHT and isatoic anhydride ISA.

As bleach activators, compounds which are aliphatic under perhydrolysis conditions Peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, can be used. Are suitable Substances which contain O- and / or N-acyl groups of said C atom number and / or Gege also bear substituted benzoyl groups. Preference is given to multiply acylated alkylene diamine, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesul fonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5- dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), and enol esters as well acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated  Sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetyl-fructose, tetraacetylxylose and octaacetyl lactose and acetylated, optionally N-alkylated glucamine and gluco nolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam. Hydrophilic sub substituted acyl acetals and acyl lactams are also preferably used. Also Combinations of conventional bleach activators can be used. The Bleach activators are commonly used in automatic dishwashing detergents in amounts of from 0.1 to 20 wt .-%, preferably from 0.25 to 15 wt .-% and in particular from 1 to 10 wt .-%, respectively based on the agent used. In the context of the present invention, the mentioned proportions on the weight of the entire molding.

Bleach activators from the group of the multiply acylated alkylenediamines are preferred, especially tetraacetylethylenediamine (TAED), N-acylimides, especially N- Nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile Methyl sulfate (MMA), preferably in amounts up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, especially 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-% based on the entire molded body, used.

With simultaneous use of bleaching agents and bleach activators are inventive Detergent tablets preferably in which a phase contains bleach, while at least one other phase contains bleach activators.

Other important ingredients of detergents come from the groups of surfactants, Enzymes, corrosion inhibitors, and dyes and fragrances. These substances will be described below.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for. From coconut, palm, tallow or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms, and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

Another class of preferred nonionic surfactants used either alone nonionic surfactant or used in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl ester.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N- dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the Fatty acid alkanolamides may be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than the Half of it.

Further suitable surfactants are polyhydroxy fatty acid amides of the formula (I)

wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalky group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups , The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having from 1 to 8 carbon atoms, with C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, For example, glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N Alkoxy- or N-aryloxy-substituted compounds can then be reacted with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxyfatty acid amides are transferred.  

Conversely, however, the content of individual phases or of the entire molding, d. H. all phases, on certain surfactants a positive effect can be achieved. The introduction The alkylpolyglycosides described above have proven to be advantageous, so that Detergent tablets are preferred in which at least one phase of Contains molding alkylpolyglycosides.

As already mentioned, the use of surfactants in detergent tablets is limited to The automatic dishwashing preferably on the use of nonionic surfactants in small Amounts. In the context of the present invention, preferred detergent tablets are characterized in that it has total surfactant contents below 5% by weight, preferably below 4 wt .-%, more preferably below 3 wt .-% and in particular below 2 wt .-%, each based on the weight of the molding having.

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, the automatic dishwashing detergent tablets according to the invention contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. Preferred nonionic surfactants are alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical is linear or preferably methyl-branched in the 2-position may contain or linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for. From coconut, palm, tallow or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical mean values which may be an integer or a fractional number for a particular product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Particular preference is given to detergent tablets according to the invention which are nonionic Surfactant containing a melting point above room temperature. Accordingly, are preferred detergent tablets characterized in that they are used as ingredient c) nonionic surfactant (s) having a melting point above 20 ° C, preferably above of 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, included.

Suitable nonionic surfactants, the melting or softening points in said Temperature range, are, for example, low-foaming nonionic surfactants, which may be solid or highly viscous at room temperature. Become at Room temperature highly viscous nonionic surfactants used, it is preferred that these have a viscosity above 20 Pas, preferably above 35 Pas and especially above 40 Pas respectively. Nonionic surfactants, which have waxy consistency at room temperature, are also prefers.

Preferred nonionic surfactants to be used at room temperature are from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures These surfactants with structurally complicated surfactants such as Polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) - Nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, this is the nonionic surfactant with a melting point above room temperature, an ethoxylated nonionic surfactant which is derived from the Reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, more preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.

A particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

The nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25% by weight, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated Monohydroxyalkanols or alkylphenols which additionally contain polyoxyethylene-polyoxypropylene Have block copolymer units. The alcohol or alkylphenol part such Nonionic surfactant molecules preferably make up more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such Nonionic surfactants.

Further particularly preferred nonionic surfactants with melting points above Room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene Block polymer blends containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a Block copolymers of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants which may be used with particular preference are for example under the name Poly Tergent® SLF-18 from Olin Chemicals available.

Further preferred detergent tablets according to the invention contain nonionic surfactants of the formula

R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ],

in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x ≧ 2, each R ³ in the above formula may be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x ≧ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is to

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

As enzymes come in the detergent tablets according to the invention in particular those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic acting enzymes, amylases, glycosyl hydrolases and mixtures of said enzymes in Question. All of these hydrolases contribute to the removal of stains such as protein, grease and or starchy stains. For bleaching, oxidoreductases can also be used become. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens as well from their genetically modified variants derived enzymatic agents. Preferably, subtilisin-type proteases, and in particular, proteases derived from Bacillus lentus are used. Here are enzyme mixtures, for example Protease and amylase or protease and lipase or lipolytic enzymes or from Protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but in particular protease and / or lipase-containing Mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Also Peroxidases or oxidases have proven to be suitable in some cases. To the Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and Pectinases.

The enzymes may be adsorbed to carriers or embedded in encapsulating substances to them to protect against premature decomposition. The proportion of enzymes, enzyme mixtures or For example, enzyme granules may contain about 0.1 to 5 wt%, preferably 0.5 to about 4.5 wt%. be. In the context of the present invention preferred Detergent tablets are characterized in that they protease and / or amylase contain.

The fact that the detergent tablets according to the invention can contain the enzyme (s) in different phases makes it possible to provide tablets with very precisely defined enzyme release and action. The table below gives an overview of possible enzyme distributions in inventive two-phase detergent moldings:

Phase 1 Phase 2 AL = L <amylase AL = L CB = 3 <Protease @ AL = L CB = 3 <Lipase @ AL = L CB = 3 <Amylase + Protease @ AL = L CB = 3 <Amylase + Lipase @ AL = L CB = 3 <Protease + Lipase @ AL = L CB = 3 <amylase + protease + lipase @ amylase Proteaase lipase Amylase + protease Amylase + lipase Protease + lipase Amylase + protease + lipase amylase amylase protease amylase Amylase + protease amylase amylase protease protease protease Amylase + protease protease amylase Amylase + protease protease Amylase + protease Amylase + protease Amylase + protease lipase amylase Amylase + lipase amylase Protease + lipase amylase Amylase + protease + lipase amylase lipase protease Amylase + lipase protease Protease + lipase protease Amylase + protease + lipase protease lipase Amylase + protease Amylase + lipase Amylase + protease Protease + lipase Amylase + protease Amylase + protease + lipase Amylase + protease

If the enzymes are used only in one phase of the moldings according to the invention, then they are Preference is given to detergent tablets in which the enzyme (s) are not in one phase is included together with the bleach-enhancing active ingredient combination.

The separation of the bleaching agent from the enzymes is hereby preferred. Detergent shaped bodies, which are characterized in that at least one phase Bleach contains, while at least one other phase contains enzymes are also preferred embodiments of the present invention.

The cleaning agents according to the invention can be used to protect the items to be washed or the machine Corrosion inhibitors, with particular silver protectants in the range of machine dishwashing have a special meaning. Can be used, the known Substances of the prior art. In general, especially silver protectants can be selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the Alkylaminotriazole and the transition metal salts or complexes can be used. Especially Preferred to use are benzotriazole and / or alkylaminotriazole. One finds in In addition, cleaning formulations often include active chlorine-containing agents that corrode the Silver surface can significantly reduce. In chlorine-free cleaners become special Oxygen and nitrogen-containing organic redox-active compounds, such as two and trivalent phenols, e.g. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, Phloroglucin, pyrogallol or derivatives of these classes of compounds. Likewise Zinc compounds are used to prevent corrosion on the items to be washed.  

If the detergent tablets contain corrosion inhibitors, these are preferred by the Bleaches separately. Accordingly, detergent tablets are those in which at least one phase contains bleach while at least one other phase Contains corrosion inhibitor, preferably.

In order to facilitate the disintegration of highly compressed moldings, it is possible Disintegration aids, so-called tablet disintegrants to incorporate into this, the Shortening disintegration times. Among tablet disintegrants and decay accelerators are According to Römpp (9th edition, Bd. 6, p. 4440) and Voigt "textbook of the Pharmaceutical Technology "(6th edition, 1987, pp. 182-184) understood excipients that are responsible for rapid disintegration of tablets in water or gastric juice and for the release of the drugs in absorbable Take care of the form.

These substances, which are also referred to as "explosives" due to their effect, increase their size when water enters its volume, whereby on the one hand increases the intrinsic volume (swelling), on the other hand, a pressure can be generated by the release of gases, which the Tablet disintegrates into smaller particles. Well-known disintegration aids are For example, carbonate / citric acid systems, although other organic acids can be used. Swelling disintegration aids are for example synthetic Polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified Natural products such as cellulose and starch and their derivatives, alginates or casein derivatives.

Preferred detergent tablets contain from 0.5 to 10% by weight, preferably from 3 to 7% by weight. and in particular 4 to 6% by weight of one or more disintegration aids, in each case based on the molding body weight. Contains only the basic shaped body Disintegration aids, the information given relates only to the weight of the product Basic tablet. In the incorporation of disintegration aids in the Detergent components of the invention include those as ingredient d).

Preferred disintegrating agents are used in the context of the present invention Cellulosic disintegrating agents used so that preferred Detergent tablet such a cellulose-based disintegrant in amounts of 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-%.  

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.

The cellulose used as disintegration aid is preferably not in finely divided Form used, but before adding to the premixes to be pressed into a coarser form converted, for example, granulated or compacted. Washing and Detergent tablets, the disintegrators in granular or optionally cogranulated Are contained in the German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and international patent application WO 98/40463 (Henkel) described. These documents are also granular details of the production, compacted or cogranulated cellulose explosive. The particle sizes Such disintegrating agents are usually above 200 μm, preferably at least 90% by weight. between 300 and 1600 microns and in particular at least 90 wt .-% between 400 and 1200 μm. The abovementioned and described in more detail in the cited documents coarser disintegration aids based on cellulose are within the scope of the present invention Invention preferably used as a disintegration aid and commercially for example available under the name Arbocel® TF-30-HG from Rettenmaier.  

Another cellulose-based disintegrant or as part of this component Microcrystalline cellulose can be used. This microcrystalline cellulose is going through partial hydrolysis of celluloses obtained under such conditions that only the amorphous Areas (about 30% of the total cellulose mass) of the celluloses attack and completely Dissolve the crystalline areas (about 70%) but leave undamaged. A subsequent one Disaggregation of the resulting by the hydrolysis micro-fine celluloses provides the microcrystalline celluloses having primary particle sizes of about 5 microns and For example, to granules with an average particle size of 200 microns are compacted.

In the context of the present invention, preferred detergent tablets are included additionally a disintegration aid, preferably a disintegration aid Cellulose base, preferably in granular, cogranulated or compacted form, in quantities from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight. %, in each case based on the molding weight.

The detergent tablets according to the invention can moreover have a containing gas-developing effervescent system. The gas-developing effervescent system can from a consist of a single substance which releases a gas on contact with water. Under these Compounds is in particular the magnesium peroxide mentioned, which when in contact with water Oxygen releases. Usually, however, the gas-releasing bubbling system is in turn of at least two components that react with each other to form gas. While here a variety of systems is thinkable and executable, for example, nitrogen, oxygen or release hydrogen, which is in the washing and Detergent moldings used Sprudelsystem both on the basis of economic and be selected on the basis of ecological criteria. Preferred effervescent systems consist of Alkali metal carbonate and / or bicarbonate and an acidifying agent, the is suitable to release carbon dioxide from the alkali metal salts in aqueous solution.

In the case of the alkali metal carbonates or bicarbonates, the sodium and potassium salts are for reasons of cost compared to the other salts clearly preferred. Of course you have to not the respective pure alkali metal carbonates or bicarbonates are used; Rather, mixtures of different carbonates and bicarbonates be preferred washing technical interest.  

In preferred detergent tablets, the effervescent system is 2 to 20% by weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or -hydrogencarbonats and 1 to 15, preferably 2 to 12 and especially 3 to 10 wt. % of an Acidifizierungsmittels, in each case based on the entire molding used.

As Acidifizierungsmittel that release carbon dioxide from the alkali salts in aqueous solution, are, for example, boric acid and alkali metal hydrogen sulfates, Alkali metal dihydrogen phosphates and other inorganic salts. To be favoured However, organic Acidifizierungsmittel used, wherein the citric acid is a particularly preferred acidifying agent. In particular, the other fixed ones can be used Mono-, oligo- and polycarboxylic acids. Again preferred from this group are tartaric acid, Succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid as well Polyacrylic acid. Organic sulfonic acids such as sulfamic acid are also usable. Commercially available and as Acidifizierungsmittel in the context of the present invention Also preferably used is Sokalan® DCS (trademark of BASF), a mixture of Succinic acid (max 31 wt%), glutaric acid (max 50 wt%) and adipic acid (max 33 wt%).

In the context of the present invention, detergent tablets are preferred in which as the acidifying agent in the effervescent system, a substance from the group of organic di-, tri- and oligocarboxylic acids or mixtures of these can be used.

In addition, the automatic dishwashing agents according to the invention in tablet form Colorings and perfumes are added to the aesthetic impression of the resulting products to improve the consumer's performance in addition to the visual and sensory "typical and unmistakable "product as perfume oils or fragrances can individual fragrance compounds, eg. B. the synthetic products of the ester type, Ethers, aldehydes, ketones, alcohols and hydrocarbons are used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p- tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, Linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and Benzylsalicylate. Ethers include, for example, benzyl ethyl ether, to the aldehydes z. B. the linear alkanals with 8-18 C atoms, citral, citronellal,  Citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the Ketones z. As the Jonone, α-Isomethylionon and Methylcedrylketon, to the alcohols anethole, Citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the Hydrocarbons mainly include the terpenes such as limonene and pinene. Prefers However, mixtures of different fragrances are used, which together a create an appealing scent. Such perfume oils can also be natural fragrance mixtures contained in plant sources, e.g. Pine, citrus, jasmine, Patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, Chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, Vetiver oil, Olibanum oil, Galbanum oil and Labdanum oil and Orange blossom oil, Neroliol, Orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the moldings according to the invention but may also be advantageous to apply the fragrances on carriers. As such Support materials, for example, cyclodextrins have proven useful, the cyclodextrin Perfume complexes can be additionally coated with other excipients. Also an incorporation of the fragrances as ingredient d) in the inventive Detergent components is possible and leads to a fragrance impression when opening the Machine.

In order to improve the aesthetic impression of the agents according to the invention, it may (or parts thereof) with suitable dyes. Preferred dyes, their selection the expert no difficulty, have a high storage stability and Insensitivity to the other ingredients of the agent and against light and none pronounced substantivity to the substrates to be treated with the agents, such as glass, Ceramic or plastic utensils, so as not to stain them. In particular, the coloring individual phases for optical differentiation is preferred.

The production of the shaped body according to the invention is initially carried out by the dry Mixing the components of the individual phases, which are pre-granulated in whole or in part can, and then informing, in particular pressing into tablets, wherein Conventional methods for producing multiphase moldings are used can. To produce the multiphase shaped bodies according to the invention, the  Premixes in a so-called matrix between two stamps to a fixed Comprimat compacted. This process, which is referred to below as tabletting, is divided divided into four sections: metering, compaction (elastic deformation), plastic deformation and Ejecting.

The tableting is carried out in commercial tablet presses, which in principle with single or Double stamping can be equipped. In the latter case, not only the upper punch used for pressure build-up, and the lower punch moves during the pressing operation the upper punch, while the upper punch presses down. For small Production quantities are preferably used eccentric tablet presses in which the or the punches are attached to an eccentric disc, which in turn on an axis with a certain rotational speed is mounted. The movement of this ram is with the Operation of a conventional four-stroke engine comparable. The compression can with one each Upper and lower stamp done, but it can also several stamps on one Eccentric disc be attached, the number of die holes extended accordingly is. The throughputs of eccentric presses vary according to type from a few hundred to a maximum 3000 tablets per hour.

For larger throughputs you can choose rotary tablet presses, where on a so-called Matrizentisch a larger number of matrices is arranged in a circle. The number of Matrices vary between 6 and 55 depending on the model, although larger dies are also commercially available are available. Each die on the die table is assigned a top and bottom stamp, in turn, the pressing pressure active only by the upper or lower punch, but also by both stamps can be set up. The die table and the stamps move around one common vertical axis, with the stamps using rail-like Curved tracks during the circulation in the positions for filling, compaction, plastic Deformation and ejection are brought. In the places where a particularly serious Raising or lowering of the stamp is required (filling, compression, ejection), These curves are through additional low pressure pieces, Nierderzugschienen and Supporting lifts supported. The filling of the die takes place via a rigidly arranged Feeding device, the so-called filling shoe, with a reservoir for the Premixes is connected. The pressing pressure on the respective premix is on the pressing paths individually adjustable for upper and lower punches, whereby the pressure build-up by the Rolling of the stamp shank heads on adjustable pressure rollers happens.  

Concentric presses can be used to increase throughput even with two or more Füllschuhen be provided. For the production of two- and multi-layered molded body several filling shoes arranged one behind the other, without the slightly pressed first layer before the further filling is ejected. By suitable process control are in this way also shell and point tablets produced, which have a onion-bowl-like structure, in the case of the point tablets, the top of the core or core layers is not is covered and thus remains visible. Rotary tablet presses are also available with single or Can be equipped with multiple tools, so that, for example, an outer circle with 50 and an inner Circle with 35 holes used simultaneously for pressing. The throughputs more modern Rotary tablet presses amount to more than one million tablets per hour.

Tableting machines suitable for the purposes of the present invention are, for example available from Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Presses GmbH, Berlin, Mapag Maschinenbau AG, Berne (CH) and Courtoy N.V., Halle (BE / LU). Particularly suitable is, for example, the hydraulic double pressure HPF 630 of the company LAEIS, D.

The moldings can be made in a predetermined spatial form and predetermined size being always made up of several phases, i. H. Layers, inclusions or cores and Rings exist. As a form of space come practically all useful manageable configurations considered, for example, the training as a blackboard, the bar or bar form, cubes, Block and corresponding room elements with flat side surfaces and in particular cylindrical embodiments with a circular or oval cross-section. This last one Design covers the presentation form of the tablet up to compact Cylinder pieces with a height to diameter ratio above 1.

The portioned compacts can each as separate individual elements be formed, the predetermined dosage of the detergent and / or detergent equivalent. However, it is also possible to form briquettes, a plurality of such Connect mass units in a compact, in particular by predetermined Predetermined breaking points the easy separability of portioned smaller units is provided. For the use of textile detergents in machines of the type common in Europe with horizontal  arranged mechanics may be the formation of portioned compacts as tablets, in Cylindrical or cuboid shape be useful, with a diameter / height ratio in Range of about 0.5: 2 to 2: 0.5 is preferred. Commercial Hydraulic Presses, Ex Center presses or rotary presses are suitable devices in particular for Production of such compacts.

The spatial form of another embodiment of the moldings is in their dimensions of Einspülkammer adapted from commercial household washing machines, so that the Moldings without dosing can be metered directly into the dispenser, where they are dissolves during the flushing process. Of course, but also a use of Detergent tablets on a dosing easily possible.

Another preferred multiphase molding that can be made has one plate-like or tabular structure with alternately thick long and thin short segments, so that individual segments of this "multi-phase bar" at the predetermined breaking points, the represent short thin segments, aborted and entered into the machine can. This principle of the "bar-shaped" detergent body can also in other geometric shapes, such as vertical triangles, the only one their sides are connected together, be realized. Here it is For optical reasons, the triangle base, which connects the individual segments, as form a phase while the triangle peak forms the second phase. A Different staining of both phases is particularly attractive in this embodiment.

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be detected by the measurand of the diametric breaking load. This is determinable

Here, σ stands for the diametrical fracture stress (DFS) in Pa, P is the force in N which leads to the pressure exerted on the molding, which causes the breakage of the  Form body caused, D is the molding diameter in meters and t is the height of Moldings.

A further subject of the present invention is a process for the production of or multi-phase detergent tablets, which builders, bleach and optionally contain other detergent ingredients by per se known pressing different particulate premixes, wherein at least one of the individual Premixes a bleach-enhancing active ingredient combination of a water-soluble salt a divalent transition metal selected from cobalt, iron, copper and ruthenium and mixtures thereof, a water-soluble ammonium salt, an inert carrier material and optionally a peroxygen-based oxidizing agent, wherein the content the bleach-enhancing active ingredient combination in the individual premixes, based on the Weight of the premix, is different.

With regard to preferred embodiments of the method according to the invention, mutatis mutandis mutandis to the above statements on the moldings of the invention to get expelled. In particular, processes are preferred in which the content of the individual premixes of the bleach-enhancing active ingredient combination, in each case based on the weight of the premixes by more than 0.0001% by weight, preferably by more than 0.001% by weight and in particular by more than 0.01% by weight.

This leads to particularly preferred process variants according to the invention, which are characterized are characterized in that two premixes pressed into a two-layer molded body with a premix, based on its weight, more than 0.0001% by weight, preferably more than 0.001% by weight and in particular more than 0.01% by weight, of bleach-enhancing active ingredient combination, while the other premix based on its weight is less than 0.01% by weight, preferably less than 0.001% by weight, especially preferably less than 0.0001% by weight and in particular 0% by weight, of the bleach-enhancing Contains active ingredient combination.

In the context of the present invention preferred detergent tablets are by Pressing particulate premixes from the bleach-enhancing active ingredient combination, the bleach and the builder system and at least one post-blended  obtained powdered component. The drug combination can be over usual Granulation processes such as mixer and plate granulation, fluidized bed granulation, extrusion, Pelleting or compaction are made. It is for the later ones Detergent molded article advantageous if the premixes to be compressed a Have apparent bulk density, which comes close to the usual compact detergent. In particular it is preferred that the premix to be compressed has a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular above 700 g / l. Another Advantage may be from a narrower particle size distribution of the premixes used result. In the context of the present invention, methods are preferred in which the Pre-mixed particle sizes between 10 and 4000 μm, preferably between 100 and 2000 μm and in particular between 600 and 1400 microns.

Before the compression of the particulate premix to detergent tablets may the masterbatch be "powdered" with finely divided surface treatment agents. This can for the nature and physical properties of both the premix (Storage, compression) and the finished detergent tablets be advantageous. Fine particulate powdering agents are well known in the art, with mostly zeolites, Silicates or other inorganic salts are used. Preference is given to the premix however, "powdered" with finely divided zeolite, with faujasite-type zeolites being preferred. In the context of the present invention, the term "faujasite-type zeolite" denotes all three zeolites forming the faujasite subgroup of the zeolite structure group 4 (cf. Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 92). In addition to the zeolite X are therefore zeolite Y and faujasite as well Mixtures of these compounds can be used, wherein the pure zeolite X is preferred. Also mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, which do not necessarily belong to the zeolite structure group 4 are as powdering agents can be used, wherein it is advantageous if at least 50 wt .-% of the powdered from a faujasite-type zeolite.

In the context of the present invention, detergent tablets are preferred which consist of a particulate premix consisting of the granular components and subsequently contains admixed powdery substances, wherein the or one of the subsequently admixed powdery components a faujasite-type zeolite with particle sizes below  100 microns, preferably below 10 microns and especially below 5 microns and at least 0.2 wt .-%, preferably at least 0.5 wt .-% and in particular more than 1 wt .-% of the constituting the compressing premix.

The finely divided treatment components with the above particle sizes can while being dry admixed to the pre-mix to be compressed. It is also possible and preferably by adding small amounts of liquid to the surface of the "stick" coarser particles. These powdering methods are wide in the art described and familiar to the expert. As liquid components that are used to Adhesion promoters of the powdering agents are suitable, for example, nonionic surfactants or aqueous solutions of surfactants or other detergent ingredients be used. In the context of the present invention it is preferred as liquid Adhesive between finely divided powdering agent and the coarse particle perfume use.

In summary, methods are preferred in which at least one, preferably all particulate premix (s) has a bulk density of at least 500 g / l, preferably has at least 600 g / l and in particular at least 700 g / l /, wherein particulate premixes are preferred in which at least 50 wt .-%, preferably at least 70% by weight and in particular at least 90% by weight of the particle particle sizes from 100 to 2000 μm, preferably from 200 to 1600 μm and in particular from 400 to 1200 μm respectively.

The use of bleach-enhancing active ingredient combination of the type described above in Multi-phase detergent tablets is not described in the prior art. That this Use in certain conditions with regard to the phase split to advantageous Properties, was also unknown. Another subject of the present Invention is therefore the use of bleach-enhancing drug combinations a water-soluble salt of a divalent transition metal selected from cobalt, Iron, copper and ruthenium and mixtures thereof, a water-soluble ammonium salt, an inert carrier material and, if appropriate, an oxidizing agent. 00227 00070 552 001000280000000200012000285910011600040 0002019959589 00004 00108 peroxygen basis in multi-phase detergent tablets for automatic dishwashing.

Claims (18)

1. Two- or multi-phase detergent tablets for automatic dishwashing, containing builders, bleaches and optionally other detergent ingredients, characterized in that it additionally comprises a bleach-enhancing active ingredient combination of a water-soluble salt of a divalent transition metal selected from cobalt, iron, copper and ruthenium and their Mixtures containing a water-soluble ammonium salt, an inert carrier material and optionally a peroxygen-based oxidizing agent, wherein the content of the bleach-enhancing active ingredient combination in the individual phases, based on the weight of the phase, is different. 2. detergent molding according to claim 1, characterized in that it the bleach-enhancing active ingredient combination in amounts of 0.0001 to 10 wt .-%, preferably from 0.001 to 5% by weight, more preferably from 0.005 to 2.5 and in particular from 0.01 to 1 wt .-%, in each case based on the molding weight, contains. 3. Detergent tablet according to one of claims 1 or 2, characterized that the content of the individual phases of the bleach-enhancing active ingredient combination more than 0.0001 wt .-%, preferably by more than 0.001 wt .-% and in particular to more than 0.01 wt .-%, each based on the weight of the phase varies. 4. detergent molding according to one of claims 1 to 3, characterized in that at least one phase contains the bleach-enhancing drug combination while at least one other phase is free of the bleach-enhancing active ingredient combination. 5. detergent molding according to one of claims 1 to 4, characterized in that the shaped body further contains enzyme (s), wherein the enzyme (s) is not in one phase is included together with the bleach-enhancing active ingredient combination. 6. detergent tablets according to one of claims 1 to 5, characterized in that the phases are in the form of layers, it being preferred that the Detergent molded article comprises two or three, preferably two layers.   7. detergent tablets according to one of claims 1 to 6, characterized in that the bleach-enhancing active ingredient combination 0.01 wt .-% to 1 wt .-%, in particular 0.1 wt.% To 0.5 wt .-% transition metal, each based on the Active ingredient combination containing, wherein drug combinations are preferred in which the Transition metal salt is a Co salt, especially cobalt (II) chloride. 8. detergent molding according to one of claims 1 to 7, characterized in that the bleach-enhancing active ingredient combination 0.5 wt .-% to 25 wt .-%, in particular 1% by weight to 10% by weight of ammonium salt, in each case based on the combination of active substances, contains, wherein drug combinations are preferred in which the ammonium salt Ammonium halide, sulphate, carbonate, bicarbonate, phosphate, phosphonate, nitrate, perchlorate and / or citrate. 9. detergent molding according to one of claims 1 to 8, characterized in that the bleach-enhancing active ingredient combination 1 wt .-% to 20 wt .-%, in particular 2 wt .-% to 10 wt .-% of peroxide-based oxidizing agent, each based on the Active ingredient combination containing, wherein drug combinations are preferred in which the Oxidizing agent is alkali metal perborate and / or alkali metal percarbonate. 10. Detergent tablet according to one of claims 1 to 9, characterized in that the bleach-enhancing active ingredient combination as an inert carrier material alkali metal sulfate, alkali carbonate, alkali metal chloride, alkali metal silicate or mixtures thereof, wherein the sodium salts are preferred. 11. Detergent tablet according to one of claims 1 to 10, characterized one phase contains bleach while at least one other phase Contains bleach activators. 12. detergent tablets according to one of claims 1 to 11, characterized that at least one phase contains bleach, while at least one other phase Contains enzymes.   13. detergent tablets according to one of claims 1 to 12, characterized that at least one phase contains bleach, while at least one other phase Contains corrosion inhibitor. 14. A process for producing two- or multi-phase detergent tablets, which Builders, bleaches and optionally other detergent ingredients, by per se known compression of different particulate premixes, characterized in that at least one of the individual premixes a Bleach-enhancing combination of a water-soluble salt of a divalent transition metal selected from cobalt, iron, copper and ruthenium and mixtures thereof, a water-soluble ammonium salt, an inert Contains support material and optionally a peroxide-based oxidant, wherein the content of the bleach-enhancing active ingredient combination in the individual Premixes, based on the weight of the premix, is different. 15. The method according to claim 14, characterized in that the content of the individual Premixes to the bleach-enhancing active ingredient combination, in each case based on the Weight of the premixes by more than 0.0001% by weight, preferably by more than 0.001% by weight and in particular by more than 0.01% by weight. 16. The method according to any one of claims 14 or 15, characterized in that two Premixes are pressed into a two-layer molding, with a Premix, based on its weight more than 0.0001 wt .-%, preferably more than 0.001 wt .-% and in particular by more than 0.01 wt .-%, the bleach-enhancing Active ingredient combination contains, while the other premixture based on its weight less than 0.01% by weight, preferably less than 0.001% by weight, more preferably less than 0.0001% by weight, and especially 0% by weight, of the bleach-enhancing Contains active ingredient combination. 17. The method according to any one of claims 14 to 16, characterized in that at least a, preferably all particulate premix (s) a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l / have, wherein particulate premixes are preferred in which  at least 50% by weight, preferably at least 70% by weight and in particular at least 90% by weight of the particles have particle sizes of from 100 to 2000 μm, preferably from 200 to 1600 microns and in particular from 400 to 1200 microns have. 18. Use of bleach-enhancing active compound combinations of a water-soluble A divalent transition metal salt selected from cobalt, iron, copper and Ruthenium and mixtures thereof, a water-soluble ammonium salt, an inert Carrier material and optionally a peroxide-based oxidant in Multi-phase detergent tablets for automatic dishwashing.